Diazo-3-trifluoromethyl-4-tertiaryaminobenzene compounds

ABSTRACT

Improved light sensitivity and dye forming coupling speed are obtained in one-component diazo-type copying material useful in preparing intermediate diazo-type reproducible copies through the use as the light-sensitive component a 1-diazo-3-trifluoromethyl4-tertiary-amino-benzene compound.

United States Patent Inventors Georg Werner;

Herbert Rauhut, both of Wiesbaden- Biebrich, Germany Appl. No. 529,650

Filed Feb. 24, 1966 Patented Oct. 26, 1971 Assignee Keuffel & Esser Company Morristown, NJ.

Priority Feb. 24, 1965 Germany K 55375 DIAZO-3-TRlFLUOROMET11YL-4- TERTIARYAMINOBENZENE COMPOUNDS 7 Claims, No Drawings U.S. Cl 96/91 R,

96/49, 96/75, 260/141, 260/142, 260/247.5 R, 260/293 D, 260/326.85, 260/570.5 R

Int. Cl C07cl13/00, C07d 29/00, G03c 1/52 Field of Search 96/49, 75,

[56] References Cited UNITED STATES PATENTS 2,350,843 6/1944 Vanselow et a] 96/91 2,298,444 10/1942 Weissberger et al.. 96/91 2,552,354 5/1951 Von Glahn et al.... 96/91 2,793,118 5/1957 Sanders et a] 96/75 X 3,218,300 11/1965 Kullmar et a1. 260/141 X 3,251,889 5/1966 Kulka 260/141 X 3,357,968 12/1967 Wilbert et al. 260/141 X FOREIGN PATENTS 895,250 5/1962 Great Britain 96/91 957,838 5/1964 Great Britain 96/91 Primary Examiner Floyd D. Higel A!t0rneys.|. Russell Juten, Peter F. Willig and Milford A.

Juten ponent a l-diazo-3-trifluoromethyl-4-tertiary-amino-benzene compound.

DIAZO-3-TRIFLUOROMETHYL-4- TERTIARYAMINOBENZENE COMPOUNDS general formula I Nix (I) In this formula I, R and R stand for alkyl, aralkyl or cycloalkyl, R for hydrogen or halogen atom, and X for an anion.

These diazo compounds, when developed with one of the usual developers having pH values of 8 to 10 and containing phloroglucinol or resorcinol as coupling components, generally yield brown azo dyes when R; in Formula I is halogen, and black azo dyes when R is hydrogen and R is aralkyl.

The alkaline developers which contain polyvalent phenols as coupling components having the disadvantage that they do not keep for long because oxidation by the air sets in. For this reason, in recent times, developers are used having pH values below 8 which correspond to neutral or, preferably, acid reaction, and containing polyvalent phenols as coupling components.

For the successful use of acid developers, diazo compounds with great coupling activity are necessary. As such, compounds of formula ll as known:

1112K (II) In this formula II, R, stands for a phenylacetoamido, thiophenylacetoamido, benzoylacetoamido-arylmercapto, alkoxyphenyl or benzoylamino group, and R and R stand for alkyl, aralkyl or aryl.

The coupling dyes which are achieved with acid developers in combination with the diazo compounds of formula II are in general of black colors and those achieved in combination with the rapid-coupling compounds of formula I are of violet hues. In fact, the commercially available diazo-type papers for acid development do only give copies with black or with violet lines. For this reason, diazo compounds which, when developed with acid developers, yield colors other than those mentioned above, are of great interest for practical purposes. The reason for this is not only that the consumer is accustomed for example to brown lines from alkaline development, but also because brown dyes on transparent supports absorb ultraviolet light particularly well.

It was now found that with diazotype material which contains, as light-sensitive substance in the reproduction coating, a diazo compound corresponding to the general formula [11 (III) wherein R and R stand for alkyl, aralkyl or cycloalkyl groups which may be substituted or not, or R, and R together with the nitrogen form a heterocyclic ring, and X is an anion, redbrown to brown-red, even brown-orange, coupling dyes of excellent covering power are obtained when acid developers are used. The diazo compounds according to formula III are distinguished by very great coupling activity, which is of advantage also when alkaline developers are used.

The diazo compounds of formula [,named in British Pat. specification No. 711,380 among others, wherein an alkyl group stands for R do, after exposure of the reproduction coating sensitized with them, also yield images with brown hues when acid developers are used. However, their coupling activity and the covering power of the coupling dyes is lower than in the case of the corresponding compounds of formula III with a CF group in place ofR In German Pat. No. 1,015,679, among other compounds, the chlorostannate of l-diazo-4-monocyclohexylamino-3- trifluoromethyl-benzene is mentioned. This compound, as a secondary amino diazo compound, is not so light sensitive as the diazo compounds of formula III which bear a tertiary amino group in p-position to the diazo group. Moreover, when development is effected with acid developers, it gives violetblack hues which do not cover so well.

The diazo compounds according to formula III may be prepared according to various methods. Their synthesis is particularly simple when a process is used which is another object of the present invention. In this process, 2-chloro-5-nitro-I- trifluoromethylbenzene is used as starting material and this is reacted with a secondary amine of the formula NHR R wherein R and R have the meaning given above, for example dimethylamine, diethylamine, diisopropylamine-di-n-butylamine, hydroxyethylpropylamine, methylbenzylamine, hydroxyethylbenzylamine, methylcyclohexylamine, pyrrolidine, morpholine, thiomorpholine, piperidine, N-alkylpiperazine, N-acylpiperazine. In the case of the secondary amines used for the reaction, the alkyl, cycloalkyl and aralkyl groups or the heterocyclic ring may bear substituents which behave inert in the reaction. The nitro group of the resulting nitroaminotrifluoromethylbenzene with a tertiary amino group is then reduced to the amino group, the amino group is diazotized according to known methods, the anion X is added in the form of a soluble compound comprising the anion X, and in an amount sufficient to precipitate at least part of the formed diazonium compound as a salt of the above formula. Finally, the precipitated salt is separated from the remainder of the reaction mixture.

The diazo compounds obtained after diazotation may be separated in the form of the chlorides as double salts with zinc chloride, cadmium chloride, stannic chloride, or as sulfates, borofluorides, hexafluorophosphates. The form in which the compound is present after separation has little influence on the property of the diazo compound. The diazo compounds according to formula III have good compatibility with the stabilizing agents usual in sensitizing solutions, such as 1,3,6-or 1,3,7-naphthalenetrisulfonic acid, boric acid, tartaric acid, citric acid, and others.

As support materials for the diazo reproduction coating according to the invention, photocopying base paper, precoated photocopying base paper, transparent paper, transparentized paper, transparent paper provided with a coating of cellulose acetate which has been made hydrophilic, plastics films, e.g. polyester films or polycarbonate films, suitably pretreated for use as diazotype coating supports, can be used. Diazotype material which contains a diazo compound of formula Ill as light-sensitive substance in the reproduction coating, cannot only be used with acid developers but can also be developed in alkaline manner. The hues achieved are in general light brown to yellowish brown.

Diazo compounds according to formula III, whose coupling intensity is less great, can also be used for the preparation of so-called two-component diazotype material. Depending on the nature of the coupling component used together with EXAMPLE 1 As base paper suitable for the preparation of diazo-type material and which had previously been provided with a precoat of colloidal silicic acid and polyvinyl acetate was coated on the precoated side with a solution which contained in 1,000 parts by volume of water:

5.0 parts by weight of citric acid 36.0 parts by weight of sodium naphthalene-l,3,6-trisulfonate,

0.5 parts by weight of saponine 50.0 parts by volume of isopropanol 26.0 parts by weight of the diazo compound from l-amino- 4-methylbenzylamino-3-trifluoro-methylbenzene as borofluoride.

After drying of the applied solution, the sensitized paper was imagewise exposed under a transparent original and developed with a solution which in 1,000 parts by volume of water contained:

3.0 parts by weight of phloroglucinol 960 parts by weight of trisodium citrate 24.2 parts by weight of sodium benzoate 19.7 parts by weight of adipic acid 57.0 parts by weight of sodium chloride 2.0 parts by weight of sodium salt of alkylnaphthalenesulfonic acid, e.g. the product marketed under the trademark Nekal A.

The pH value of the developer is 6. Brown images on a white background were obtained.

When, instead of the diazo compound used above, there was used in the sensitizing solution the diazo compound from l-amino-4-methylbenzylamino-3-methylbenzene, violet images on a white background were obtained. After application of the developer, the violet coupling dye was formed but distinctly more slowly than when the diazotype material according to the invention was used.

EXAMPLE 2 Transparent paper which is coated on one side with a partially saponified cellulose acetate coating was coated on the precoated side with the sensitizing solution described in example 1, exposed under a line original after drying, and treated as in example 1. Brown-red lines with good covering power were obtained. In this case, too, the dye formed very rapidly directly after application of the developer.

EXAMPLE 3 Base paper without a precoat and which is suitable as coating support for the preparation of diazotype material, was coated with a solution which contained in 1,000 parts by volume ofwater:

5.0 parts by weight of citric acid 36.0 parts by weight of sodium naphthalene-1,3,6-trisulfonate 50.0 parts by volume ofisopropanol 25.0 parts by volume of triglycol 1.0 part by weight of saponine 25.0 parts by weight of the diazo compound from l-amino- 4-piperidino-3-trifluoromethyl-benzene as borofluoride.

After drying of the applied solution, the sensitized base paper was image-wise exposed under a transparent line original and developed with a solution which, in 1,000 parts by volume of water, contained the following substances and had a pH value of6.3:

57.0 parts by weight of potassium adipate 23.0 parts by weight of sodium benzoate 1.0 part by weight of adipic acid 5.0 parts by weight of thiourea 5.0 parts by weight of cane sugar 6.5 parts by weight of phloroglucinol 4.0 parts by weight of resorcinol 2.0 parts by weight of sodium salt of alkylnaphthalenesul- 5 fonic acid, e.g. the product marketed under the trademark Nekal A. Copies with red-brown lines on a white background were obtained.

When the sensitized paper was developed with a solution which contained in 1,000 parts by volume of water:

20.0 parts by weight of borax 20.0 parts by weight of trisodium phosphate 40.0 parts by weight of trisodium citrate 6.0 parts by weight of resorcinal 6.0 parts by weight of phloroglucinol 30.0 parts by weight of thiourea 2.0 parts by weight of the sodium salt of alkylnaphthalenesulfonic acid, e.g. the product marketed under the trademark Nekal A. Copies in neutral brown hues on a white background were obtained.

When the diazo compound from l-amino-4-morpholino-3- trifluoromethylbenzene was used as light-sensitive substance in the reproduction coating of the diazotype paper, under the same conditions, with the two developers mentioned above, copies with yellowish hues were obtained.

EXAMPLE 4 An already precoated diazotype base paperof the type mentioned in example 1 was coated on the precoated side with a solution which contained in 1,000 parts by volume of water:

40.0 parts by weight of citric acid 40.0 parts by weight of thiourea 26.0 parts by weight of7hydroxynaphthimidazole-1,2

50.0 parts by volume of isopropanol 25.0 parts by volume of triglycol 20.0 parts by volume of glacial acetic acid 38.5 parts by weight of diazo compound from l-amino-4- pyrrolldino-3-trifluoromethyl-benzene as zinc chloride double salt.

After drying of the applied solution, the thus obtained sensitized paper was image-wise exposed under a transparent line original and developed with ammonia vapor. Copies with redbrown lines on a white background were obtained.

The table following the next paragraph gives several representative diazo compounds according to formula Ill.

It is apparent that the described examples are capable of many variations and modifications within the scope of the present invention. All such variations and modifications are to be included within the scope of the present invention.

/C2H5 45 N 01 2 C4Ho O1 L N\ 2 iHsu CH3 BFA 62-63 N CH3 BF; 76 E C2H4OH 01 ZnCl N 2 BF 11 N H o 1 BF4 51 N H CI-ZnClrHCl 59 N H N-CHa CI-ZnCl; '160 N H N-COCHa 1 Melting point of the Corresponding amino compound.

4. Diazotype material according to claim 1 wherein said diazo compound is 1-diazo-4-morpholino-3-trifluoromethylbenzyl diazonium borofluoride.

5. Diazotype material according to claim 1 wherein said diazo compound is l-diazo-4-pyrrolidino-3-trifluoromethylbenzyl diazonium zinc chloride.

6. Diazo compound corresponding to the general formula wherein R and R are selected from the group consisting of lower alkyl, hydroxy alkyl, aralkyl, cyclohexyl radicals, and heterocyclic radicals in which R,, R and the nitrogen atom form 5- or 6-membered nitrogen-containing heterocyclic radicals, and heterocyclic radicals, and X stands for an anion.

7. 4( N-pyrrolidino)-3-trifluoro methyl aniline.

* :k k w 

2. Diazotype material according to claim 1 wherein said diazo compound is 1-diazo-4-methylbenzylamino-3-trifluoromethylbenzene-diazonium borofluoride.
 3. Diazotype material according to claim 1 wherein said diazo compound is 1-diazo-4-piperidino-3-trifluoromethylbenzene diazonium borofluoride.
 4. Diazotype material according to claim 1 wherein said diazo compound is 1-diazo-4-morpholino-3-trifluoromethylbenzyl diazonium borofluoride.
 5. Diazotype material according to claim 1 wherein said diazo compound is 1-diazo-4-pyrrolidino-3-trifluoromethylbenzyl diazonium zinc chloride.
 6. Diazo compound corresponding to the general formula
 7. 4(N-pyrrolidino)-3-trifluoro methyl aniline. 